CN106659153B - Solid herbicidal composition containing safener - Google Patents

Abstract

A solid herbicidal composition in granular form is provided comprising pyroxsulam and cloquintocet acid. These solid herbicidal compositions have excellent storage stability, are prepared in a simple and efficient manner, and are readily wetted, dispersed and form stable suspensions in cold water.

Description

Solid herbicidal composition containing safener

Background technique

Agricultural formulation products must be physically and chemically stable for a specified period of time to be commercially useful. Formulations are unstable for many reasons, including active ingredient instability (eg, chemical degradation of the active ingredient), physical instability such as phase separation (Ostwald ripening, crystallization, sedimentation, emulsion stratification, etc.) or environmental factors (temperature, humidity/moisture, etc.). In today's pesticide market, it is common to develop new formulations containing multiple active ingredients, safeners and/or excipients, etc. to achieve optimal profiles, efficacy and delivery efficiency, thus making formulation development more challenging .

SUMMARY OF THE INVENTION

A solid herbicidal composition is provided. Solid herbicidal compositions include:

a) from about 50 grams of active ingredient per kilogram (g ai/kg) to about 600 g ai/kg of pyroxsulam relative to the total composition;

b) about 50 g ai/kg to about 600 g ai/kg of cloquintocet acid relative to the total composition;

c) about 30 g ai/kg to about 250 g ai/kg of lignosulfonate relative to the total composition;

d) from about 10 g/kg to about 100 g/kg of anionic surfactant relative to the total composition; and

e) From about 50 g/kg to about 250 g/kg of solid buffer relative to the total composition.

Methods of making the solid herbicidal compositions described herein are also described.

Detailed ways

This application describes solid herbicidal compositions comprising pyroxsulam, cloquintocet acid or a salt thereof (herbicide safener); a dispersant; an anionic surfactant; and a solid buffer. These solid herbicidal compositions may be in the form of granules, eg, water-dispersible granules. The solid herbicidal compositions described herein have excellent storage stability and can be prepared in a simple and efficient manner. In some embodiments, the composition is physically and chemically stable for 4 weeks at 54°C. Solid herbicidal compositions readily wet, decompose, disperse and form stable suspensions in water, even cold water (eg, 5°C). The solid herbicidal compositions described herein may be in the form of extruded granules that are stable during storage at elevated temperatures, rapidly wet, decompose and disperse in cold water to form a stable suspension. Additionally, the solid herbicidal compositions described herein maintain herbicidal action and crop safety when applied by spray application for controlling weeds in cereal crops.

The solid herbicidal composition includes pyroxsulam. The solid herbicidal compositions described herein may comprise from about 50 grams of active ingredient per kilogram (g ai/kg) to about 600 g ai/kg of one or more pyroxsulams relative to the total composition . In some embodiments, the solid herbicidal compositions described herein may comprise from about 50 g ae/kg to about 500 g ae/kg, from about 50 g ae/kg to about 400 g ae/kg, from about 50 g ae/kg to about 300 g ae/kg kg, about 50 g ae/kg to about 200 g ae/kg, about 50 g ae/kg to about 150 g ae/kg, or about 50 g ae/kg to about 100 g ae/kg of pyroxsulam. In some embodiments, the solid herbicidal compositions described herein may comprise from about 100 g ae/kg to about 600 g ae/kg, from about 150 g ae/kg to about 600 g ae/kg, from about 150 g ae/kg to about 500 g ae/kg /kg, about 150 g ae/kg to about 400 g ae/kg, about 150 g ae/kg to about 350 g ae/kg, about 150 g ae/kg to about 300 g ae/kg, about 150 g ae/kg to about 250 g ae/kg, About 200g ae/kg to about 600g ae/kg, about 250g ae/kg to about 600g ae/kg, about 250g ae/kg to about 500g ae/kg, about 300g ae/kg to about 500g ae/kg, about 350g ae/kg to about 475 g ae/kg, about 400 g ae/kg to about 475 g ae/kg, or about 430 g ae/kg to about 460 g ae/kg of pyroxsulam.

The solid herbicidal compositions described herein also include cloquintocet acid (CQC acid) or a salt thereof. CQC acid is a herbicide safener with the following chemical structure:

CQC acids are used as herbicide safeners by reducing the phytotoxic effects of herbicides on applied crops. In some embodiments, the herbicide safener used in the solid herbicidal compositions described herein may comprise a salt of cloquintocet acid comprising one or more cations selected from the group consisting of sodium, potassium And organoammonium cations, where the organoammonium cation can have from 1 to about 12 carbon atoms. Exemplary organic ammonium cations include, for example, isopropylammonium, diethylene glycol ammonium (2-(2-aminoethoxy)ethanolammonium), dimethylammonium, diethylammonium, triethylammonium, monoethylammonium Ethanolammonium, Dimethylethanolammonium, Diethanolammonium, Triethanolammonium, Triisopropanolammonium, Tetramethylammonium, Tetraethylammonium, N,N,N-Trimethylethanolammonium (choline), and N,N-bis-(3-aminopropyl)methylammonium (BAPMA).

The herbicide safener for use in the solid herbicidal compositions described herein may comprise from about 50 g ae/kg to about 600 g ae/kg of cloquintocet acid or a salt thereof relative to the total composition. In some embodiments, the herbicide safener may comprise about 50 g ae/kg to about 300 g ae/kg, about 50 g ae/kg to about 200 g ae/kg, about 50 g ae/kg to about 150 g ae/kg, about 50 g ae/kg to about 125 g ae/kg, about 50 g ae/kg to about 100 g ae/kg, about 50 g ae/kg to about 80 g ae/kg, or quinoxyacetic acid ( cloquintocet acid) or their salts. In some embodiments, the herbicide safener may comprise about 100 g ae/kg to about 600 g ae/kg, about 150 g ae/kg to about 600 g ae/kg, about 200 g ae/kg to about 600 g ae/kg, about 200 g ae/kg /kg to about 500g ae/kg, about 200g ae/kg to about 400g ae/kg, about 200g ae/kg to about 350g ae/kg, about 200g ae/kg to about 300g ae/kg, about 200g ae/kg To about 250 g ae/kg, or about 200 g ae/kg to about 225 gae/kg of cloquintocet acid or a salt thereof. In some embodiments, the herbicide safener may comprise from about 300 g ae/kg to about 600 g ae/kg, from about 350 g ae/kg to about 500 g ae/kg, from about 400 g ae/kg to about 500 g ae/kg, or about 425 g ae/kg to about 475 g ae/kg of cloquintocet acid or a salt thereof.

In some embodiments, the ae-based weight ratio of cloquintocet acid safener or salts thereof to one or more herbicidal active ingredients in the solid herbicidal compositions described herein may be about 10: 1 to about 1:10, about 5:1 to about 1:5, about 4:1 to about 1:4, about 3:1 to about 1:3, or about 2:1 to about 1:2.

H、O、T和F，

25M以及

88B、825，所有均可购自MeadWestvaco(Richmond,VA)；

NA、CA和3A，其可购自Borregaard LignoTech(Houston,TX)。The solid herbicidal compositions described herein further include a dispersant such as a lignosulfonate. Examples of lignosulfonates include sodium lignosulfonate and/or calcium lignosulfonate. Examples of lignosulfonate dispersants suitable for use with the solid herbicidal compositions described herein include

H, O, T and F,

25M and

88B, 825, all available from MeadWestvaco (Richmond, VA);

NA, CA and 3A, which are available from Borregaard LignoTech (Houston, TX).

Dispersants for use in the solid herbicidal compositions described herein may comprise from about 30 g/kg to about 250 g/kg, relative to the overall composition. In some embodiments, the solid herbicidal compositions described herein may include about 30 g/kg to about 230 g/kg, about 30 g/kg to about 210 g/kg, about 30 g/kg to about 190 g/kg, about 30 g/kg kg to about 170g/kg, about 30g/kg to about 150g/kg, about 30g/kg to about 130g/kg, about 30g/kg to about 110g/kg, about 30g/kg to about 90g/kg, about 30g/kg kg to about 70 g/kg, about 30 g/kg to about 50 g/kg, or about 30 g/kg to about 40 g/kg of dispersant. In some embodiments, the solid herbicidal compositions described herein may also include about 50 g/kg to about 250 g/kg, about 75 g/kg to about 250 g/kg, about 75 g/kg to about 225 g/kg, about 75 g /kg to about 200g/kg, about 75g/kg to about 175g/kg, about 100g/kg to about 175g/kg, about 125g/kg to about 175g/kg, about 145g/kg to about 165g/kg, about 75g /kg to about 125 g/kg, or about 85 g/kg to about 115 g/kg of dispersant.

Anionic surfactants for use in the solid herbicidal compositions described herein may include at least one anionic surfactant selected from those specifically described in: "McCutcheon's Detergents and Emulsifiers Annual," MC Publishing Corp., Ridgewood , New Jersey, 1998 and "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81. Suitable anionic surfactants may be selected from: salts of alkyl sulfates such as diethanolammonium lauryl sulfate; alkylarylsulfonates such as calcium dodecylbenzenesulfonate; soaps such as sodium stearate ; Alkylnaphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate; Salts of dialkyl sulfosuccinates, such as the sodium salt of bis(2-ethylhexyl)sulfosuccinate; N-alkyl -N-fatty acid taurates; salts of mono- and di-alkyl phosphates; and polycarboxylates, such as sodium polycarboxylate.

T-77，可购自Solvay Rhodia(Houston,TX)。In some embodiments, the anionic surfactants used in the solid herbicidal compositions described herein may include N-alkyl-N-fatty acid taurate surfactants, such as N-methyl-N-olene Sodium taurine, which is

T-77, available from Solvay Rhodia (Houston, TX).

T-36(Solvay Rhodia)。In some embodiments, the anionic surfactants used in the solid herbicidal compositions described herein may include sodium polycarboxylate surfactants, such as

T-36 (Solvay Rhodia).

The solid herbicidal compositions described herein may include from about 10 g/kg to about 100 g/kg of at least one anionic surfactant. In some embodiments, the solid herbicidal compositions described herein may include about 10 g/kg to about 90 g/kg, about 10 g/kg to about 80 g/kg, about 10 g/kg to about 70 g/kg, about 10 g/kg kg to about 60 g/kg, about 10 g/kg to about 50 g/kg, about 10 g/kg to about 40 g/kg, about 10 g/kg to about 30 g/kg, about 20 g/kg to about 50 g/kg, or about 20 g /kg to about 40 g/kg of at least one anionic surfactant. In some embodiments, the solid herbicidal compositions described herein may include about 20 g/kg to about 100 g/kg, about 30 g/kg to about 100 g/kg, about 40 g/kg to about 100 g/kg, about 50 g/kg kg to about 100 g/kg, about 60 g/kg to about 100 g/kg, about 70 g/kg to about 100 g/kg, or about 70 g/kg to about 90 g/kg of at least one anionic surfactant.

The solid buffers used in the solid herbicidal compositions described herein are generally readily soluble in water (>20 wt%) and may include organic or inorganic acids, or their salts. Examples of solid buffers include ammonium sulfate, diammonium phosphate, citric acid, potassium acetate, sodium acetate, and combinations of solid buffers and clays.

The solid herbicidal compositions described herein may include from about 50 g/kg to about 250 g/kg of solid buffer. In some embodiments, the solid herbicidal compositions described herein may include about 60 g/kg to about 240 g/kg, about 70 g/kg to about 230 g/kg, about 80 g/kg to about 220 g/kg, about 90 g/kg kg to about 210 g/kg, about 100 g/kg to about 200 g/kg, about 110 g/kg to about 190 g/kg, about 120 g/kg to about 180 g/kg, about 130 g/kg to about 170 g/kg, or about 140 g /kg to about 160 g/kg of solid buffer. In some embodiments, the solid herbicidal compositions described herein may also include about 50 g/kg to about 250 g/kg, about 50 g/kg to about 200 g/kg, about 50 g/kg to about 175 g/kg, about 50 g /kg to about 150 g/kg, about 50 g/kg to about 125 g/kg, about 50 g/kg to about 100 g/kg, about 50 g/kg to about 90 g/kg, about 50 g/kg to about 80 g/kg, or about 50 g/kg to about 70 g/kg of solid buffer.

The agricultural granules containing the active ingredient may also contain solid inert ingredients which may act as fillers, diluents, carriers, disintegrants, binders, processing aids and/or flow aids and may assist in maintaining The particles are in a stable solid state. These solid inert ingredients may include, for example, clays, starch, silica, talc (hydrated magnesium silicate), attapulgite, pyrophyllite, attapulgite clay, kaolinite clay, bentonite clay, montmorillonite clay, illite Stone clays and fuller's earth, and diatomaceous earths such as diatomite, tripolite and kieselgur/kieselguhr, carbohydrates such as dextrins, alkanes Alkylated cellulose, xanthum gums and gums, and synthetic polymers such as polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyvinyl pyrrolidone and urea/aldehyde polymers. In the absence of effective solid inert ingredients, dry particles can be physically unstable and slowly decompose to form dusts or powders. Many solid inert ingredients used in agricultural granule formulations generally have good water solubility or dispersibility.

In some embodiments, the solid herbicidal compositions described herein may include fillers selected from one or more of the following clays: eg attapulgite clay, kaolinite clay, bentonite clay, montmorillonite clay , illite clay and fuller's earth.

M，其可购自Albemarle Corporation(Baton Rouge,LA)，以及它们的混合物。In some embodiments, the solid herbicidal compositions described herein may include synthetic polymers selected from the group consisting of polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, and urea/aldehyde copolymers, such as

M, which is commercially available from Albemarle Corporation (Baton Rouge, LA), and mixtures thereof.

M，其可以用作崩解剂和加工助剂。In some embodiments, the solid herbicidal compositions described herein may include synthetic polymers, such as urea/aldehyde copolymers, such as

M, which can be used as a disintegrant and a processing aid.

The term "stable" when used to describe the compositions described herein refers to compositions that are physically and/or chemically stable over a specified period of time to the environment in which the composition is prepared, shipped, and/or stored. Aspects of stable compositions include, but are not limited to, physical stability at temperatures from about 0°C to about 50°C, ease of wetting, disintegration, dispersion and formation of stable suspensions when poured into water and when applied to target pests, for example, by spraying compositions that retain their biological efficacy over time, and compositions that contain active ingredients that do not degrade chemically in significant amounts.

In some embodiments, the solid herbicidal compositions described herein are stable at a temperature of greater than or equal to about 40°C for a period of at least 2, 4, 6, or 8 weeks. In some embodiments, the solid herbicidal compositions described herein are stable at a temperature of greater than or equal to about 54°C for a period of at least about 2 or 4 weeks.

In some embodiments, the solid herbicidal compositions described herein are stored in a closed container at a temperature of at least about 30°C, at least about 40°C, at least about 50°C or at least about 54°C for at least about 2, 4, 6 or Stable after 8 weeks.

In some embodiments, the solid herbicidal compositions described herein readily wet, decompose, disperse and form stable suspensions in cold water at a temperature of equal to or less than about 5°C, equal to or less than about 10°C, equal to or less than about 15°C, or equal to or less than about 20°C.

The physical stability of a solid agricultural composition after storage at the temperatures and conditions described herein can be determined by (1) measuring the time it takes for the composition to completely disperse upon addition to water (ie, dispersion time), (2) measuring The stability of the resulting suspensions (ie the total suspension rate of the samples was measured) and those values for the samples were compared with those measured for the corresponding samples prior to storage. As used herein, "completely dispersed" refers to the disintegration of particles into suspended particles. The particle size can vary, but in some embodiments, the particle size is a few microns, eg, 3-10 microns.

The dispersion time of a solid composition is a measure of the time it takes for the composition to wet, break down, and completely disperse in water, and can be readily determined using the methods described herein. The stability of a suspension formed when a solid composition is dispersed in water can be determined by measuring how much of the sample remains in suspension after a period of time (ie, total suspension). The total suspension of the sample can be determined using the CIPAC method 184. In some embodiments, the solid herbicidal compositions described herein are in less than about 80 seconds, less than about 70 seconds in room temperature water having a hardness of 342 ppm after storage at a temperature equal to or greater than room temperature, 30° C., 40° C., or 50° C. , less than about 60 seconds, less than about 50 seconds, less than about 40 seconds or less than about 30 seconds, easily wet, decomposed and completely dispersed into suspended particles.

In some embodiments, the solid herbicidal compositions described herein are easily wetted, decomposed, dispersed and form stable suspensions in room temperature water with a hardness of 342 ppm after storage at a temperature equal to or greater than room temperature, 30° C., 40° C., 50° C. liquid, the total suspension rate of the suspension is not less than about 80%, not less than about 85%, not less than about 90%, not less than about 92%, not less than about 94%, not less than about 95%, not less than about 96%, not less than about 97%, not less than about 98%, or not less than about 99%, as determined using the CIPAC method 184.

The present application also describes methods of making the solid herbicidal compositions. Granular formulations can be prepared using one or more of the following processing methods: (1) pan granulation, (2) mixing agglomeration, (3) extrusion granulation, (4) fluid bed granulation, (5) ) spray granulation or aggregation, (6) drum granulation. In addition, granules can be prepared using a pellet press. The physicochemical properties of the active ingredients and additives are considered important when choosing the method of use. G.A. Bell and D.A. Knowles in, "Chemistry and Technology of Agrochemical Formulations," D.A. Knowles, editor, (Kluwer Academic Publishers, 1998), pages 41-114, describe particle species for agrochemical formulations, and provide a number of refer to. Powder formulations can be prepared by vacuum drying, rotary evaporator drying, spray drying, drum drying, or other processing methods known to those skilled in the art. In any of the processing methods described herein, optional inert ingredients may be added to the composition before, during, or after processing to improve the process or to improve the final quality or stability of the granules or powder. These optional inert ingredients may include, but are not limited to, flow additives and anti-caking agents such as hydrophilic precipitated silica, hydrophilic fumed silica and clays, antifoaming agents, wetting agents, binding agents agent, dispersant, solid diluent and carrier.

In one embodiment, the solid herbicidal composition can be prepared by a method comprising:

(1) combining the dry ingredients and air-mixing them;

(2) adding water to the air-kneaded dry ingredients;

(3) mixing the air-milled dry ingredients and water to form a paste (or extrudate);

(4) extruding the paste (or extrudate) to provide extruded pellets; and

(5) Drying the extruded granules to provide the solid herbicidal composition.

Another aspect of the solid herbicidal composition includes adding one or more additional pesticidal active ingredients, plant growth regulators or safeners to the solid herbicidal composition. These pesticidal active ingredients, plant growth regulators and safeners may include one or more of herbicides, insecticides, fungicides, plant growth regulators or herbicide safeners.

Suitable additional herbicides that may be added to the solid herbicidal compositions described herein include ALS enzyme inhibitor herbicides and compounds of the formula:

in

Ar represents phenyl, which is substituted with one to four substituents independently selected from the group consisting of: halogen, _C1 - _C6 alkyl, _C1 - _C6 alkoxy, C2 _{- C4} alkane Oxyalkyl, C ₂ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ haloalkoxy, C ₂ -C ₄ haloalkoxyalkyl , C ₂ -C ₆ haloalkylcarbonyl, C ₁ -C ₆ haloalkylthio, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -OCH ₂ O- and -OCH ₂ CH ₂ O-;

R means H or F;

X represents Cl or vinyl;

Y represents Cl, vinyl or methoxy; and

their salts and esters.

Further examples of suitable additional herbicides that may be added to the solid herbicidal compositions described herein include clodinafop-propargyl, clethodim, cycloxydim, clodinafop-methyl ( diclofop-methyl), oxadifen + isoxidifen-ethyl, pinoxaden, sethoxydim, tepraloxydim, tralkoxydim, 2,4- 2,4-D esters and amines, 2,4-2 methyl 4 chloride (2,4-MCPA), 2,4-2 methyl 4 chloride esters and amines (2,4-MCPA esters and amines) , acetochlor, acifluorfen, alachlor, amidosulfuron, aminopyralid, aminotriazole, thiocyanate Ammonium thiocyanate, anilifos, azimsulfuron, benfuresate, bensulfuron, bensulfuron-methyl, bensulfuron bentazone, bentazone-sodium, benthiocarb, benzobicyclon, benzofenap, bifenox, bispyribac-sodium, bromobutide, butachlor, cafenstrole, carfentrazone-ethyl, chlorimuron, chlorsulfuron, chlorfenapyr (chlorpropham), cinosulfuron, clomazone, clomeprop, clopyralid, cloransulam, cloransulam Cloransulam-methyl, cumyluron, cyclosulfamuron, daimuron, diclosulam, diflufenican, dimep iperate), pentoxazine (dimethametryn), diquat (diquat), dithiopyr (dithiopyr), EK2612, epindimethalin (EPTC), esprocarb (esprocarb), diflufenapyr (ET-751), ethbenzanid, ethoxysulfuron, fenoxasulfone, fentrazamide, flazasulfuron, florasulam, fluazifop, fenoxasulfone flucetosulfuron, flufenacet, flufenpyr-ethyl, flumetulam, flumioxazin, flupyrsulfuron, chloro fluroxypyr, fluroxypyr esters and salts, fomesafen, foramsulfuron, glufosinate, glufosinate Phosphine (glufosinate-P), glyphosate (glyphosate), halosulfuron-methyl (halosulfuron-methyl), imazamox (imazamethabenz), imazamox (imazamox), imazapic (imazapic), imazamox (imazapyr), imazaquin, imazethapyr, imazosulfuron, indanofan, iodosulfuron, ioxynil, ipfencarbazone, iso isoxaben, 2-methyl-4-chlorobutyric acid (MCPB), mefenacet, mesosulfuron, mesotrione, chloropyrazine Metazosulfuron, metolachlor, metosulam, molinate, monosulfuron, sodium methylarsulfuron (MSMA), nicosulfuron (nicosulfuron), orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, ethoxy oxyfluorfen (oxyfluorfen), paraquat (paraquat), pendimethalin (pendimethalin), penoxsulam (penoxsulam), pentoxazone (pentoxazone), picloram (picloram) piperophos), pretilachlor, primisulfuron-methyl, prohexadione-calcium, propachlor, propanil, propisochlor , propyrisulfuron, propyzamide, prosulfuron, pyrabuticarb, pyraclonil, pyrazogyl, pyrazolynate, ethyl pyrazolyl pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, algaecide Quinoclamine, quinclorac, rimsulfuron, S-3252, simazine, simetryne, s-metolachlor ), sulcotrione, sulfentrazone, sulfosate, sulphosulphuron, tefuryltrione, thenylchlor, thiazopyr, thiosulphuron thifensulfuron, thiobencarb, triafamone, tribenuron, triclopyr, triclopyr-esters and amines, trifloxysulfuron , Trifluralin, trinexapac-ethyl and tritosulfuron.

Additional examples of additional herbicides (and their salts or esters) that may be added to the solid herbicidal compositions described herein include, for example, the compounds disclosed in US Pat. Nos. 7,314,849 B2; 7,300,907 B2; 7,786,044 B2;

In some embodiments, the herbicide is a compound of the formula:

or _C1 - _C6 alkyl esters or salts thereof, eg methyl esters, also known as halauxifen-methyl.

In some embodiments, the herbicide is a compound of the formula:

or a C ₁ -C ₁₂ alkyl ester or a C ₇ -C ₁₂ aryl alkyl ester or salt thereof, such as a benzyl ester, referred to herein as compound A.

The compositions and methods described herein can be applied in combination with glyphosate, glufosinate, dicamba, phenoxy auxin ( phenoxyauxins), pyridyloxy auxins, aryloxyphenoxypropionates, acetyl CoA carboxylase (ACCase) inhibitors, imidazolidinones (imidazolinones), acetolactate synthase (ALS) inhibitors (acetolactate synthase (ALS) inhibitors), 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors (4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors), Protoporphyrinogen oxidase (PPO) inhibitors, triazines and bromoxynil; the crops are glyphosate-tolerant crops, glufosinate-tolerant crops sex crops, dicamba tolerant crops, phenoxy auxin tolerant crops, pyridyloxy auxin tolerant crops, aryloxyphenoxy propionate tolerant crops, ACCase tolerant Crops, imidazolinone tolerant crops, ALS tolerant crops, HPPD tolerant crops, PPO tolerant crops, triazine tolerant crops, bromoxynil tolerant crops having the ability to confer resistance Multiple or additive properties of one chemical property and/or multiple modes of action.

Suitable pesticides that may be added to the solid herbicidal compositions described herein include abamectin, acephate, acetamiprid, acrinathrin, alpha- Alpha-cypermethrin, alpha-endosulfan, azadirachtin, azinphos-ethyl, azinphos-methyl, bendiocarb, propionate Benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bufencarb, thiophene Buprofezin, butacarb, carbaryl, carbofuran, carbosulfan, cartap, cartap hydrochloride, Chlorantraniliprole, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos-methyl, cyclamate chromafenozide, clothianidin, cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, diazinon, paclitaxel Phosphorus (dicrotophos), diflubenzuron (diflubenzuron), dimethoate (dimethoate), dinotefuran (dinotefuran), disulfoton, emamectin (emamectin), emamectin benzoyl Emamectin benzoate, endosulfan, endothion, endrin, fenthiophos (EPN), esfenvalerate, etaphos, fendicarb ( ethiofencarb), ethion, ethipro le), ethoate-methyl, etofenprox, fenamiphos, fenazaflor, fenethacarb, fenitrothion, bufencarb (fenobucarb), fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fenvalerate fipronil), flonicamid, flubendiamide, flucythrinate, fonofos, fufenozide, furathiocarb, gamma-cyhalothrin cyhalothrin), lindane (gamma-HCH), halfenprox, halofenozide, heptenophos, hyquincarb, imidacloprid, indoxacarb ( indoxacarb, isazofos, isobenzan, isocarbophos, isofenphos, isofenphos-methyl, isoprocarb, leaf Isothioate, isoxathion, kinoprene, lambda-cyhalothrin, lepimectin, lufenuron, malathion, Methomyl, methoxyfenozide, mevinphos, mexacarbate, milbemectin, nitenpyram, fenflumuron ( novaluron), omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, penfluron, benzyl chloride permethrin, phenthoate, phorate, phosalone, phosfolan, Phosmet, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, primidophos ), profenofos, profluthrin, promecarb, propaphos, propoxur, prothiofos, pymetrozine, pyrafluprole, acetamiprid (pyridalyl), pyrifluquinazon, pyriprole, pyriproxyfen, spinetoram, spinosad, spirotetramat, sulfoxaflor , sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin ), tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocyclam, thiocyclam oxalate, sulfur thiodicarb, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, azole tolfenpyrad, triazophos, triflumuron and zeta-cypermethrin.

Suitable fungicides that may be added to the solid herbicidal compositions described herein include tricyclazole, phthalide, carpropamide, pyroquilon, diclocymet , fenoxanil, probenazole, isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamycin (kasugamycin), flutolanil, mepronil, pencycuron, polyoxins, validamycin, toclophos-methyl, Niacinamide (boscalid), penthiopyrad (penthiopyrad), thifluzamide (thifluzamide), bixafen, fluopyram (fluopyram), isopyrazam (isopyrazam), propiconazole (propiconazole), phenyl ether Difenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin, pyraclostrobin ( orysastrobin) and activated ester (acibenzolar-S-methyl). Some of these fungicides may not be effective for disease control when applied at the timing of herbicide granule application because the spread and growth cycle of the fungal disease may not match the target weed growth cycle. Effective uses and timing of application of these fungicides can be readily determined by those skilled in the art.

Suitable herbicide safeners that may be added to the solid herbicidal compositions described herein include benoxacor, benthiocarb, cloquintocet-mexyl, daimuron, alkene Dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, Harpin Protein, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetrinil (MG 191), MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoic acid amide.

Suitable plant growth regulators that may be added to the solid herbicidal compositions described herein include 2,4-D (2,4-D), 2,4-D butyric acid (2,4-DB), indoleacetic acid (IAA), indole butyric acid (IBA), naphthaleneacetamide, α-naphthaleneacetic acid, kinetin, zeatin, ethephon, aviglycine , 1-methylcyclopropene (1-MCP), ethephon, nine-two O (gibberellins), gibberellic acid, S-abscisic acid, cyclopropene Proprimidol (ancymidol), furoprimidol (flurprimidol), mefluidide (mefluidide), paclobutrazol (paclobutrazol), tetracyclacil (tetcyclacis), uniconazole (uniconazole), brassinolide (brassinolide) , ethyl brassinolide (brassinolide-ethyl) and ethylene (ethylene).

In addition to the compositions and uses described above, the solid herbicidal compositions described herein may also be used in combination with one or more additional compatible ingredients. Other additional compatible ingredients may include, for example, one or more agrochemical active ingredients, surfactants, dyes, fertilizers and trace elements, pheromones, and many other additional ingredients that provide utility functions such as stabilizers, fragrances, and dispersants agent. When the compositions described herein are used in combination with additional active ingredients, the claimed compositions may be formulated as herbicidal solid compositions with one or more other active ingredients, together with one or more other active ingredients Tank mix in water for spray application or sequentially with the other active ingredient(s) in a separate solid or spray application.

In addition, the solid herbicidal compositions described herein can optionally be blended with other solid compositions comprising additional active ingredients to form compositions comprising, for example, a physically homogeneous blend of granules or a physically homogeneous blend of powders mixture. These blends of solid compositions can be used to control unwanted weeds in a variety of crop and non-crop environments.

Surfactants conventionally used in formulation technology and which may optionally be used in the formulations of the present application are particularly described in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I -III, Chemical publishing Co., New York, 1980-81. These surfactants can be anionic, cationic or nonionic in nature and can be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Commonly used surfactants include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, For example, nonylphenol-C ₁₈ ethoxylates; soaps such as sodium stearate; alkylnaphthalene-sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as dibutyl naphthalene Sodium (2-ethylhexyl)sulfosuccinate; quaternary amines such as lauryltrimethylammonium chloride; block copolymers of ethylene oxide and propylene oxide; and monoalkyl phosphates and dioxane phosphates salts of base esters. Oftentimes, some of these surfactants are used instead as agricultural adjuvants, liquid carriers or surfactants.

The term herbicide as used herein refers to an active ingredient that kills, controls or otherwise adversely alters the growth of at least one plant. Herbicidally effective amounts or vegetation control amounts of herbicides are those that adversely modify the active ingredient and include amounts that deviate from natural plant development, kill, regulate, dehydrate, retard, and the like. The terms "plant" and "vegetation" include newly emerging seedlings as well as established and dormant vegetation.

The solid herbicidal compositions described herein provide acceptable herbicidal action and crop safety when applied by spray application to control weeds in cereal crops. Solid herbicidal compositions can be added to or diluted in aqueous spray mixtures for agricultural applications, eg, for selective weed control in crop fields. Such compositions are usually diluted with an inert carrier such as water before application. The diluted compositions are typically applied to, for example, the weeds, the locus of the weeds, or the locus where the weeds will eventually emerge, and in some embodiments, the diluted compositions comprise from about 0.0001 to about 1 wt% active ingredient or from 0.001 to about 0.05 wt% active Element. The compositions of the present application may be applied to, for example, weeds or weed loci by the use of conventional ground or aerial sprinklers, by addition to irrigation water, and by other conventional means known to those skilled in the art.

The following examples are given to illustrate various aspects of the compositions and methods described herein and should not be construed as limitations on the claims.

Example

Dispersion and Total Suspension Test Methods

Dispersion time measurement

a) Put 0.1g of sample particles in a 25mL beaker;

b) Add 100 mL of 342 ppm hard water to a 100 mL stoppered graduated cylinder at room temperature;

c) Pour the granules into a graduated cylinder. Start stop watch. Insert the stopper into the barrel and immediately flip 180o, then return to the original position. The entire operation is completed in about 2 seconds.

d) Repeat the above inversion at 10 second intervals thereafter. After each complete inversion, examine the sample for the presence of undispersed or undissolved particles. The sample continues to invert until all particles are dispersed or dissolved.

Total Suspension Measurement

a) Weigh out enough sample (b grams) to make 250 mL of a suspension in water at the concentration recommended in the product instructions for use.

b) Place the weighed sample in a 250 mL beaker and add about 50 mL of standard water. The mixture was manually rotated circularly for 2 minutes at a rate of 120 beats per minute.

c) Transfer the suspension into a graduated cylinder so that the previous temperature of the graduated cylinder is 20°C. Measure 250 mL at 20°C with a standard hose, and insert the stopper. Invert the cylinder 180 degrees for a total of 30 times in one minute, and then return to the original position. Place the cylinder in an upright position in the water bath, avoiding vibration and direct sunlight. After 30 minutes, the top 225 mL (9/10) of the contents was removed using a pipette within 10 to 15 seconds, being careful not to disturb the deposition in the cartridge. Make sure that the tip of the pipette is always just a few millimeters below the liquid surface.

d) Gravimetric analysis to determine the solid content in the deposit. After removing the 9/10 suspension, the remaining 1/10 suspension at the bottom of the graduated cylinder was transferred to a weighing evaporating dish by rinsing with distilled water and dried to constant weight. Record the mass of the residue to the nearest 0.01 g (a).

e) Calculation: total suspension (wt%)=111(b-a)/b, where a=dry mass (in grams) of lower 25 mL suspension; b=mass in grams for sampling test.

Preparation of representative samples of solid herbicidal compositions described herein and evaluation of storage stability Sample 1 .

F(10.00g)、

T-77(2.00g)、

M(10.00g)、高岭土粘土(5.35g)和无水柠檬酸(6.00g)。将粉末混合物混合并且穿过空气研磨机。然后将水(25-35wt％)添加至空气研磨的粉末以形成挤出物，将挤出物挤出通过蓝式挤出机。在40℃将最终挤出颗粒干燥。To the mixer was added pyroxsulam (21.50 g), cloquintocetacid (45.15 g),

F(10.00g),

T-77(2.00g),

M (10.00 g), kaolin clay (5.35 g) and anhydrous citric acid (6.00 g). The powder mixture was mixed and passed through an air mill. Water (25-35 wt%) was then added to the air-milled powder to form extrudates, which were extruded through a blue extruder. The final extruded granules were dried at 40°C.

Storage stability evaluation:

sample 2 .

F(4.00g)、

T-77(5.00g)、

M(10.00g)、高岭土粘土(3.60g)和硫酸铵(10.75g)。将粉末混合物混合并且穿过空气研磨机。将水(25-35wt％)添加至空气研磨的粉末以形成挤出物，将挤出物挤出通过蓝式挤出机。在40℃将最终挤出颗粒(0.8mm)干燥。To the mixer was added pyroxsulam (21.50 g), halauxifen-methyl (45.15 g),

F(4.00g),

T-77(5.00g),

M (10.00 g), kaolin clay (3.60 g) and ammonium sulfate (10.75 g). The powder mixture was mixed and passed through an air mill. Water (25-35 wt%) was added to the air-milled powder to form extrudates, which were extruded through a blue extruder. The final extruded pellets (0.8 mm) were dried at 40°C.

Storage stability evaluation:

The scope of the present invention is not limited to the embodiments disclosed herein, which are intended to illustrate some aspects of the present invention, and any embodiments that are functionally equivalent fall within the scope of the present invention. Various modifications to the described compositions and methods in addition to those shown and described herein will become apparent to those skilled in the art and are intended to fall within the scope of the appended claims. Furthermore, while only certain representative composition components and method steps disclosed herein have been specifically discussed in the above-described embodiments, other combinations of such composition components and method steps will be apparent to those skilled in the art. Obviously, it is also intended to fall within the scope of the appended claims. Thus, the present application may explicitly refer to a combination of components or method steps; however, a combination of components and method steps is included, although not explicitly mentioned. The terms including and its variants used in this application and the term including and its variants are used synonymously, and they are all open-ended, non-limiting terms.

Claims (3)

1. A solid herbicidal composition comprising:

a) 50 grams of active ingredient per kilogram (g ai/kg) to 600g ai/kg pyroxsulam (pyroxsulam) relative to the total composition;

b) (ii) quinoxyacetic acid (cloquintocet acid) in an amount of 50g ai/kg to 600g ai/kg relative to the total composition;

c) 30g ai/kg to 250g ai/kg lignosulfonate relative to the total composition;

d) 10 to 100g/kg of anionic surfactant, relative to the total composition;

e) 50 to 250g/kg of a solid buffer relative to the total composition, wherein the solid buffer is ammonium sulfate or citric acid; and

f) a disintegrant, wherein the disintegrant is a urea formaldehyde copolymer.

2. The solid herbicidal composition of claim 1, wherein the solid herbicidal composition is an extruded granule.

3. A method of preparing a solid herbicidal composition comprising:

a) providing the ingredients of claim 1 and combining them together, air-mixing them;

b) adding water to the air-milled ingredients;

c) mixing the air-milled ingredients and water to form an extrudate;

d) extruding the extrudate to provide an extruded particle; and

e) drying the extruded particles.